CN106543480B - A kind of sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent and preparation method thereof - Google Patents

A kind of sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent and preparation method thereof Download PDF

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CN106543480B
CN106543480B CN201610935177.XA CN201610935177A CN106543480B CN 106543480 B CN106543480 B CN 106543480B CN 201610935177 A CN201610935177 A CN 201610935177A CN 106543480 B CN106543480 B CN 106543480B
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sulfonation
starch
coking
charcoal
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CN106543480A (en
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袁利萍
胡云楚
冯斯宇
黄自知
袁光明
吴袁泊
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Central South University of Forestry and Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

A kind of sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent, the microcapsules anti-flaming smoke-inhibiting agent is made of interior embedding material and outer cladding capsule layer, wherein the interior embedding material includes the raw material of following mass fraction: 80~100 parts of phosphoric acid, 60~80 parts of cyclodextrin, 50~60 parts of starch, 200~300 parts of the concentrated sulfuric acid, 30~50 parts of crosslinking agent, 10~20 parts of urea, 2~5 parts of emulsified wax, 2~5 parts of surfactant；The outer cladding capsule layer includes the raw material of following mass fraction: Nano-meter CaCO331~2 part, 50~70 parts of melamine resin；It is the environment friendly flame retardant of a kind of high-efficiency low-toxicity.The present invention also provides the preparation methods of sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent, are conducive to the development and reuse of biological material industrial wood waste, are also beneficial to improve the interface compatibility of cyclodextrin and coated capsule layer.

Description

A kind of sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent and preparation method thereof
Technical field
The invention belongs to field of fire-proof technology more particularly to a kind of sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agents And preparation method thereof.
Background technique
Fire is that the whole world influences one of maximum natural calamity, seriously threatens people's safety of life and property.Public security The data of Fire Department of portion show that 2013, the whole nation was informed of a case fire 38.8 ten thousand altogether, dead 2113 people, injured 1637 people, direct wealth Produce 48.5 hundred million yuan of loss.Compared with 2012, fire number rises 1.52 times, and death toll rises 106%, and number of injured people rises 1.85 times, direct property loss increases 122%.Wherein, home fire occurs 11.7 ten thousand, accounts for the 30.1% of sum, causes 1215 People is dead, accounts for the 57.5% of sum, and mostly occur in house and business place compared with conflagration, direct property loss is huge.Pass through Flame retardant treatment can reduce the combustibility of combustible material, slow down the burning velocity of combustible material, smoke-producing amount be reduced, for preventing fire Generation and win quality time of Initial Stage of Fire, be all particularly significant for evacuating personnel and controlling, fight a fire in time 's.
According to statistics, having 70~80% in fire fatality number is as caused by cigarette and toxic gas asphyxia.In fire not only The a large amount of heat of release, also generates a variety of toxic gases and smog.Toxic gas causes personnel to suffocate, and smog reduces the energy in the scene of a fire Degree of opinion interferes fire fighter to enter scene of fire and rescues, the personnel of scene of fire is made to be difficult to evacuate and flee the scene, cigarette Directly it is frightened also to will cause visibility reduction, expiratory dyspnea and psychology for harm.It can be seen that cigarette and toxic gas are in fire Lead to the mostly important factor of casualties.Therefore, fire prevention research has higher requirement to fire proofing, is reducing heat Cigarette generation is reduced simultaneously.However currently, many insoluble problems are still had during material is fire-retardant.
Some researches show that fire-retardant often to make material combustion incomplete, combustion product becomes complicated, and toxic gas increases, resistance Combustion agent itself decomposition also releases noxious material.Halogen system and Sb system fire retardant fire proofing have apparent production cigarette in combustion Characteristic, APP(Efficient Wood fire retardant-ammonium polyphosphate therein) it will lead to flue gas concentration increase in fire.Wang Qing text et al. Studies have shown that FRW(phosphorus-nitrogen-boron system wood fire retardant) cigarette yield, specific extinction area, the carbon dioxide of wood treated with fire retardants be dense Degree and yield of carbon dioxide are significantly reduced than unseasoned timber, but when to combustion of wood carbon monoxide generation without significant shadow It rings.
Chinese invention patent ZL201310578624.7 discloses a kind of the polyurethane micro-encapsulated of Core-shell synergistic flame can Expanded graphite and its application in rigid polyurethane foam, polyurethane microcapsule are using expansible graphite particle as capsule Core, using the polyurethane that cyclodextrin or cyclodextrin/modified resin and toluene di-isocyanate(TDI) are cross-linked to form as softgel shell.Inflatable stone Black microcapsules can effectively improve the temperature of initial decomposition and thermal stability of material, heat release rate and total when can significantly reduce burning Heat liberation unit, but since expansible graphite has " popcorn effect ", easily form " worm " shape layer of charcoal, will affect the cause of layer of charcoal Close property and integrality, so that its protection heat-blocking action to institute's covering material can be seriously affected.Chinese invention patent ZL201210026881.5 discloses a kind of preparation method of microencapsulation phosphoric acid flame retardant, in kerosene with urea-formaldehyde or Melamine-formaldehyde prepolymer coats phosphoric acid solution, obtains microencapsulation phosphoric acid flame retardant.Wherein the substance of capsule cladding is liquid State phosphoric acid solution, its encapsulated rear mechanical property is bad, is unfavorable for the mixing and processing of capsule and polymer, and use flammable Property kerosene in polymer capsule more remnants, there are still many shortcomings.Chinese invention patent ZL 201510033594.0 A kind of functionalization cyclodextrin flame-proof polylactic acid composite material and preparation method is disclosed, by a certain proportion of cyclodextrin, phosphorous Binary acid and catalyst are added in deionized water, are heated to certain temperature after mixing, react cooling after a period of time, clearly It washes, dry, obtain functionalization cyclodextrin fire retardant, then the ratio that polylactic resin and functionalization cyclodextrin fire retardant is certain Example is mixed to get functionalization cyclodextrin flame-proof polylactic acid composite material.Obtained flame-retardant agent composite material is environmentally protective, can effectively subtract Heat release when few material combustion, but the fire-retardant composite material does not show the barriering effect of poison gas, carbon monoxide It writes, still needs to be further improved.
Therefore, research invent it is a kind of can reduce simultaneously heat and flue gas release anti-flaming smoke-inhibiting agent, be those skilled in the art just Make great efforts the direction of research and development.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one Kind of effect is ideal, simple for production and low-cost sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent and its preparation side Method.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent, the microcapsules anti-flaming smoke-inhibiting agent is by interior embedded object Material and outer cladding capsule layer composition, wherein the interior embedding material is by the raw material of following mass fraction through coking, sulfonation, load And it is made after cross-linking reaction: 80~100 parts of phosphoric acid, 60~80 parts of cyclodextrin, 50~60 parts of starch, 200~300 parts of the concentrated sulfuric acid, 30~50 parts of crosslinking agent, 10~20 parts of urea, 2~5 parts of emulsified wax, 2~5 parts of surfactant；
The outer cladding capsule layer is mixed by the raw material of following mass fraction: Nano-meter CaCO331~2 part, melamine 50~70 parts of polyimide resin.
Sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent of the invention, is halogen-free, does not also use antimony oxide to make For synergist, under heat or flame interaction, sulfonation cross linked ciclodextrines starch capsules by chemical reaction generate it is excellent every matter, Heat barrier foam shape layer of charcoal, prevents internal material from burning, therefore sulfonation cross linked ciclodextrines starch capsules flame-retardant smoke inhibition of the invention Agent is the environment friendly flame retardant of a kind of high-efficiency low-toxicity.
Above-mentioned sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent, it is preferred that the phosphoric acid is that mass concentration is 60%~80% phosphoric acid solution.
Preferably, the cyclodextrin includes alpha-cyclodextrin or beta-cyclodextrin；The crosslinking agent includes epoxy silane crosslinker Or epichlorohydrin crosslinker；The surfactant includes lauryl sodium sulfate surfactant or dodecyl benzene sulfonic acid Natrium surfactant.
Based on a total technical concept, the present invention also provides a kind of sulfonation cross linked ciclodextrines starch capsules flame-retardant smoke inhibitions The preparation method of agent, comprising the following steps:
Step 1: it after cross linked ciclodextrines starch is made in cyclodextrin and starch, is carried out at coking under the action of the concentrated sulfuric acid Reason obtains coking charcoal, and coking charcoal described in a portion carries out sulfonation and handles to obtain sulfonation coking charcoal, coking described in another part Charcoal load phosphoric acid and urea obtain load coking charcoal, then hand over the sulfonation coking charcoal, load coking charcoal and cyclodextrin Copolymerization powder is made to get interior embedding material is arrived in connection reaction；
Step 2: by melamine resin and Nano-meter CaCO33It is mixed and made into Nano-meter CaCO33Melamine pre-polymerization resin, so The interior embedding material dispersion obtained after step 1 is fallen into the Nano-meter CaCO3 of atomization afterwards3In melamine pre-polymerization resin steam fog, make Interior embedding material is by Nano-meter CaCO33Melamine pre-polymerization resin cladding is got up, and arrives micro- glue after cured drying Capsule anti-flaming smoke-inhibiting agent.
Above-mentioned preparation method, it is preferred that the step 1 specifically includes following operating procedure:
The step 1 specifically includes following operating procedure:
(1) add water after mixing cyclodextrin and starch, friendship is added after 0.5~1.0h is stirred under 40~60 DEG C of constant temperatures Join agent, with NaOH solution tune PH to 9~11, reacting after 1~2h with hydrochloric acid tune PH is 6~7, after room temperature is cooling washing to neutrality, It is dried in vacuo under the conditions of 50~60 DEG C again, 80~120 meshes is crossed after pulverizing, obtain cross linked ciclodextrines starch；
(2) concentrated sulfuric acid is added in the cross linked ciclodextrines starch obtained after step (1), is carried out under the conditions of 60~80 DEG C burnt Change 2~3h, washing obtains coking charcoal after being dried to neutrality, and the coking charcoal is divided into two parts；
(3) concentrated sulfuric acid is added in a portion coking charcoal obtained after step (2), is carried out under the conditions of 80~100 DEG C 1~2h of sulfonation obtains sulfonation coking charcoal after dry until washing to filtrate is neutrality and can't detect sulfate ion；
(4) another part coking charcoal phosphoric acid solution obtained after step (2) is impregnated into 1~2h, then under ice-water bath Urea is added to stir evenly, filtering vacuum drying obtains load coking charcoal；
(5) water is added in cyclodextrin, crosslinking agent is added after stirring 0.5~1.0h under 40~60 DEG C of constant temperatures, uses After so that it is carried out 0.5~1.0h of reaction, the sulfonation coking charcoal obtained after step (3) and step is added in NaOH solution tune PH to 9~11 Suddenly the load coking charcoal obtained after (4), is warming up to 60~70 DEG C after mixing evenly, at being dried after lump shape, mistake after pulverizing 80~120 meshes, obtain powder；
(6) emulsified wax is added in the powder obtained after step (5) and stirs 0.5~1.0h, add surfactant, used 1~2h of sonic oscillation to get arrive interior embedding material.
Preferably, the cyclodextrin includes alpha-cyclodextrin or beta-cyclodextrin；The crosslinking agent includes epoxy silane crosslinker Or epichlorohydrin crosslinker；The surfactant includes lauryl sodium sulfate surfactant or dodecyl benzene sulfonic acid Natrium surfactant.
Preferably, in the step (1), the mass fraction of cyclodextrin is 40~50 parts, the mass fraction of starch is 50~ 60 parts, the mass fraction of crosslinking agent is 20~30 parts, and the mass concentration of NaOH solution is 8~10%, and the concentration of hydrochloric acid is 0.1mol/L；
In the step (2), the mass concentration of the concentrated sulfuric acid is 70~95%, the quality of cross linked ciclodextrines starch and the concentrated sulfuric acid Than for 1:5~7；
In the step (3), the mass concentration of the concentrated sulfuric acid is 90~98%, the mass ratio of coking charcoal and the concentrated sulfuric acid be 1:6~ 8；
In the step (4), the mass concentration of the phosphoric acid solution is 60%~80%, and mass fraction is 80~100 parts； The mass fraction of the urea is 10~20 parts；The coking charcoal is porous structure；
In the step (5), the mass fraction of cyclodextrin is 20~30 parts, and the mass fraction of crosslinking agent is 10~20 parts, The mass fraction of sulfonation coking charcoal is 20~30 parts, and the mass ratio of sulfonation coking charcoal and load coking charcoal is 1:1~2, and NaOH is molten The mass concentration of liquid is 8~10%；
In the step (6), the mass fraction of powder is 60~80 parts, and the mass fraction of emulsified wax is 2~5 parts, table The mass fraction of face activating agent is 2~5 parts.
Preferably, the step 2 specifically includes following operating procedure:
A. by melamine resin and Nano-meter CaCO33PH to 8~9 is adjusted in mixing, and stirring is warming up to 70~80 DEG C, and constant temperature 1~ 2h is added curing accelerator after cooling, stirs evenly to get Nano-meter CaCO33Melamine pre-polymerization resin；
B., the interior embedding material dispersion obtained after step 1 is fallen into the Nano-meter CaCO3 of atomization3Melamine pre-polymerization resin In steam fog, make interior embedding material by Nano-meter CaCO33Melamine pre-polymerization resin cladding gets up to form coating, then with 80~ 120 DEG C of air-flow heating, solidifies the coating and is dried, and obtains the microcapsules flame-retardant smoke inhibition after cooling Agent.
Preferably, in the step a, melamine resin by melamine, 37% formalin and distilled water in mass ratio 1:2.5~3:6~7 mix；The Nano-meter CaCO33Mass fraction be 1~2 part；The quality of the melamine resin Number is 50~70 parts；The curing accelerator is resorcinol, and the additional amount of the curing accelerator is melamine resin The 1.5%~2.0% of quality；
In the step b, the mass fraction of interior embedding material is 60~80 parts, Nano-meter CaCO33Melamine pre-polymerization resin Mass fraction be 100~300 parts.
The invention also discloses a kind of sulfonation cross linked ciclodextrines starch capsules prepared by the preparation method to hinder Fire smoke suppressant.
In addition to the solid sulfonation charcoal that can must have catalytic adsorption function after cyclodextrin, starch progress sulfuric acid charing, sulfonation Outside, the biomass such as bamboo, timber are pyrolyzed, after sulfonation, also can get solid sulfonation charcoal, not only in esterification, hydrolysis, ether Change, there is in ring-opening reaction good catalytic performance, and is the good fire retarding synergist of expansion type flame retardant and promotes at charcoal Agent, and since sulfonation charcoal has certain microcellular structure, material is decomposed the small organic molecule generated have certain absorption and Trapping effect.Sulfonation charcoal is added Intumescent Retardant System and can not only be effectively reduced by the heat release rate peak value of ignition resistant substrate and total The release of CO and flue gas can be more greatly reduced in Heat liberation unit.Ring has really been arrived in use of the sulfonation charcoal in Intumescent Retardant System Green, the unification of three sources are protected, is worked along both lines.
Compared with prior art, the invention has the benefit that
1. microcapsules anti-flaming smoke-inhibiting agent of the invention uses melamine resin and Nano-meter CaCO3 for the first time3As outer cladding The material of capsule is formed so that cross linked ciclodextrines are added after sulfated cyclodextrins starch and urea, phosphoric acid load coking charcoal mixed grinding Copolymer be interior embedding raw material, while by the acid source (SO in phosphoric acid and sulfated cyclodextrins starch3H-), gas source (urea, trimerization SO in cyanamide and sulfated cyclodextrins starch3H-And C effect release gas), charcoal source (cross linked ciclodextrines starch copolymer with And the condensed-nuclei aromatics charcoal in sulfated cyclodextrins starch) be integrated in one, heat can be effectively reduced in the microcapsules anti-flaming smoke-inhibiting agent being prepared into Release, and can flue gas be inhibited to discharge significantly.
2. microcapsules anti-flaming smoke-inhibiting agent of the invention, used phosphoric acid is urging strongly for wood-fibred under fire temperature Change dehydratable flame retardant, and urea is decomposed into ammonia and CO under fire temperature2Gas, the plastics melted under fire temperature and shallow lake The coking charcoal of powder, wood-fibred, wood powder etc., in ammonia and CO2It is acutely expanded under the action of gas, forms sticky layer of charcoal, it can Effectively heat-insulated oxygen barrier protection inner layer material effectively plays fire-retardant fireproof effect, meanwhile, the sulfonation obtained after sulfonated processing is burnt Changing charcoal (sulfonation cross linked ciclodextrines starch) has efficient absorption and catalyzed conversion effect, while delaying polymer to decompose, The release by CO in ignition resistant substrate and flue gas can efficiently be reduced；Cyst material of the melamine resin as microcapsules, and it is interior Embed raw material have good compatibility, can to avoid with polar character cyclodextrin and non-polar polymer material structure not Defect caused by compatible provides strong guarantee, and microcapsules flame-retardant smoke inhibition to improve fire-retardant high polymer mechanical property Agent has non-aggressive, low cigarette, nontoxicity, thermal stability and the feature of environmental protection, be conducive to significantly improve polymeric substrate at charcoal Ability and fire protecting performance.
3. preparation method of the invention will be used for polymer matrix after the blend coking of cyclodextrin and starch, sulfonation for the first time The fire-retardant and suppression cigarette of material, coking obtains hard without crisp coking charcoal after the crosslinking of cyclodextrin starch, and using the coking of porous structure Charcoal loads phosphoric acid, urea, and simple, convenient, efficient, other than cyclodextrin, starch, many biomass castoffs can also be made It is cheap for raw material sources, be conducive to the development and reuse of biological material industrial wood waste.
4. preparation method of the invention loads the coking charcoal of phosphoric acid, urea using the processing of blending polymerization sealing technique for the first time, Polymerization enclosure method is conducive to improve the heat resistance and stability of starch and cyclodextrin in coking charcoal, reduces hygroscopicity, crosslinking agent It is embedded into starch or beta-cyclodextrin cross-linked network by way of stable chemistry key connection, the work of dispersive stress can be played With being also beneficial to improve the interface compatibility of cyclodextrin and coated capsule layer to improve the mechanical property of material.
Detailed description of the invention
Technical solution in order to illustrate the embodiments of the present invention more clearly, below will be to needed in embodiment description Attached drawing is briefly described, it should be apparent that, drawings in the following description are some embodiments of the invention, general for this field For logical technical staff, without creative efforts, it is also possible to obtain other drawings based on these drawings.
Fig. 1 is the pictorial diagram of pure epoxy resin in embodiment 2.
Fig. 2 is the pictorial diagram that the fire-retardant rear fire retarding epoxide resin of sulfonation cross linked ciclodextrines starch capsules is added in embodiment 2.
Fig. 3 is the residue figure that the calorimetric of pure epoxy resin taper is tested in embodiment 2.
Fig. 4 is that fire retarding epoxide resin is bored after sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent is added in embodiment 2 The residue figure of shape calorimetric experiment.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is done below in conjunction with Figure of description and preferred embodiment more complete Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent of the invention, the microcapsules anti-flaming smoke-inhibiting agent by Interior embedding material and outer cladding capsule layer composition, preparation method specifically comprise the following steps: that (following number is mass parts Number)
(1) suitable quantity of water is added after mixing 40 parts of beta-cyclodextrins and 60 parts of starch, stirs 0.5h under 50 DEG C of constant temperatures, Then the NaOH solution tune PH about 9~11 that mass concentration is 10% is added in 20 parts of epoxy silane crosslinkers, is added dropwise after reacting 1h 0.1mol/L hydrochloric acid tune PH about 6.5 is washed to neutrality after room temperature is cooling, then is dried in vacuo under the conditions of 60 DEG C, through pulverizing 80~120 meshes are crossed afterwards, obtain cross linked ciclodextrines starch；
(2) the cross linked ciclodextrines starch obtained after step (1), according to cross linked ciclodextrines starch: the concentrated sulfuric acid=1:7 matter The concentrated sulfuric acid for being 75% than mass concentration is added is measured, coking 2h is carried out under the conditions of 80 DEG C, is washed with deionized to neutral laggard Row drying, obtains coking charcoal, and by quality dimidiations such as the coking charcoals；
(3) the wherein carbonization at low temperature charcoal obtained after step (2), according to coking charcoal: the concentrated sulfuric acid=1:6 mass ratio is added The concentrated sulfuric acid that mass concentration is 95% carries out sulfonation 2h under the conditions of 80 DEG C, and washing to filtrate is neutrality, and can't detect sulfuric acid Until radical ion, sulfonation coking charcoal is obtained after dry；
(4) it is with mass concentration by another carbonization at low temperature charcoal (the coking charcoal used is porous structure) obtained after step (2) 60% 100 parts of dipping 1h of phosphoric acid solution, 10 parts of urea are then added under ice-water bath and is stirred evenly, and filtering vacuum drying obtains To load coking charcoal；
(5) 20 parts of beta-cyclodextrin are taken, suitable quantity of water is added, stirs 0.5h under 50 DEG C of constant temperatures, 10 parts of epoxy silicon is added The NaOH solution that alkane crosslinking agent and mass concentration are 8% is appropriate, adjusts PH to 9 or so, and after so that it is carried out reaction 0.5h, step is added (3) 30 parts of the load coking charcoal 20 parts of the sulfonation coking charcoal obtained after and obtained after step (4), is warming up to after mixing evenly 60~70 DEG C, at being dried after lump shape, 80~120 meshes are crossed after pulverizing, obtain powder；
(6) 80 parts of powder, 5 parts of the addition emulsified wax stirring 0.5h that will be obtained after step (5), adds dodecyl sulphur 5 parts of sour natrium surfactant obtains copolymerization powder, the as interior embedding material with sonic oscillation 1h；
(7) melamine, 37% formalin and distilled water are mixed by 50 parts of quality, 150 parts, 350 parts, tune pH to 8~ 9, stirring is warming up to 70 DEG C, keeps constant temperature 1h, adds Nano-meter CaCO332 parts stir evenly, and it is melamine that quality is added after cooling The curing accelerator resorcinol of polyimide resin quality 1.5~2.0%, stirs evenly to get Nano-meter CaCO33Melamine pre-polymerization tree Rouge；
(8) by 60 parts of interior embedding material obtained after step 1, dispersion falls into 120 parts of nanometers of atomization in reaction tower CaCO3In melamine pre-polymerization resin steam fog, make interior embedding material by Nano-meter CaCO33Melamine pre-polymerization resin cladding is got up It forms coating, is then heated with 80~120 DEG C of air-flow, solidify the coating and dried, after cooling to obtain the final product To evengranular microcapsules anti-flaming smoke-inhibiting agent.
Effect detection:
80 parts of pine powders, 10 parts of sulfonation charcoals and urea-formaldehyde resin adhesive are uniformly mixed with ball mill, then in hot press with 2~ 3Mpa, 120~130 DEG C are hot pressed into sheet material, and 100mm × 100mm × 10mm sample is made and tests for taper calorimetric.The cone of sample Shape calorimetric experimental result comparison such as table 1(50kW/m2Heat radiation).
Table 1: the hot smoke suppressing effect of drop of the microcapsules anti-flaming smoke-inhibiting agent that embodiment 1 obtains in wood
As shown in Table 1, after microcapsules anti-flaming smoke-inhibiting agent being added in sawdust-board, highest peak heat release when burning is than pure wood Considering plate to be worth doing reduces 165/kW/m2, average heat release rate, which reduces, surpasses 1/3, and total heat release reduces 1/4；Raw cigarette total amount is by pure sawdust The 8.28m of plate2/m2It is reduced to 1.69m2/m2, only the 20% of sawdust-board；Its carbon yield increases by 10% than pure sawdust-board.The reality It tests statistics indicate that the release of heat can be effectively reduced in sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent of the invention, and can show It lands and flue gas is inhibited to discharge, the fire-retardant of sawdust-board has effectively been accomplished to work along both lines to heat, cigarette inhibition.
Embodiment 2:
A kind of sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent of the invention, the microcapsules anti-flaming smoke-inhibiting agent by Interior embedding material and outer cladding capsule layer composition, preparation method specifically comprise the following steps: that (following number is mass parts Number)
(1) suitable quantity of water is added after mixing 40 parts of alpha-cyclodextrins and 50 parts of starch, stirs 0.5h under 50 DEG C of constant temperatures, Then the NaOH solution tune PH about 9~11 that mass concentration is 10% is added in 20 parts of epichlorohydrin crosslinkers, is added dropwise after reacting 2h 0.1mol/L hydrochloric acid tune PH about 6.5 is washed to neutrality after room temperature is cooling, then is dried in vacuo under the conditions of 60 DEG C, through pulverizing 80~120 meshes are crossed afterwards, obtain cross linked ciclodextrines starch；
(2) the cross linked ciclodextrines starch obtained after step (1), according to cross linked ciclodextrines starch: the concentrated sulfuric acid=1:6 matter The concentrated sulfuric acid for being 75% than mass concentration is added is measured, coking 3h is carried out under the conditions of 80 DEG C, is washed with deionized to neutral laggard Row drying, obtains coking charcoal, and by quality dimidiations such as the coking charcoals；
(3) the wherein carbonization at low temperature charcoal obtained after step (2), according to coking charcoal: the concentrated sulfuric acid=1:8 mass ratio is added The concentrated sulfuric acid that mass concentration is 95% carries out sulfonation 1.5h under the conditions of 80 DEG C, and washing to filtrate is neutrality, and can't detect sulphur Until acid ion, sulfonation coking charcoal is obtained after dry；
(4) it is with mass concentration by another carbonization at low temperature charcoal (the coking charcoal used is porous structure) obtained after step (2) 80% 80 parts of dipping 2h of phosphoric acid solution, 10 parts of urea are then added under ice-water bath and is stirred evenly, and filtering vacuum drying obtains To load coking charcoal；
(5) 20 parts of alpha-cyclodextrin are taken, suitable quantity of water is added, 0.5h, 15 parts of epoxychloropropane are stirred under 50 DEG C of constant temperatures The NaOH solution that crosslinking agent is added and mass concentration is 10% is appropriate, after so that it is carried out reaction 1h, obtains after addition step (3) 35 parts of the load coking charcoal 20 parts of sulfonation coking charcoal and obtained after step (4), carries out being warming up to 60~70 DEG C after mixing evenly, at It is dried after lump shape, 80~120 meshes is crossed after pulverizing, obtain powder；
(6) 80 parts of powder, 5 parts of the addition emulsified wax stirring 0.5h that will be obtained after step (5), adds detergent alkylate 5 parts of sulfonate surfactants, with sonic oscillation 2h, obtain copolymerization powder, the as interior embedding material；
(7) melamine, 37% formalin and distilled water are mixed by 70 parts of quality, 210 parts, 450 parts, tune pH to 8~ 9, stirring is warming up to 70 DEG C, keeps constant temperature 1h, adds Nano-meter CaCO332 parts stir evenly；It is melamine that quality is added after cooling The curing accelerator resorcinol of polyimide resin quality 1.5~2.0%, stirs evenly to get Nano-meter CaCO33Melamine pre-polymerization tree Rouge；
(8) by 60 parts of interior embedding material obtained after step 1, dispersion falls into 200 parts of nanometers of atomization in reaction tower CaCO3In melamine pre-polymerization resin steam fog, make interior embedding material by Nano-meter CaCO33Melamine pre-polymerization resin cladding is got up It forms coating, is then heated with 80~120 DEG C of air-flow, solidify the coating and dried, after cooling to obtain the final product To evengranular microcapsules anti-flaming smoke-inhibiting agent.
Effect detection:
In parts by weight, microcapsules anti-flaming smoke-inhibiting agent manufactured in the present embodiment and the epoxy resin of E~44 (such as Fig. 1) is (micro- Capsule anti-flaming smoke-inhibiting agent/E~44=10:90) mixed at high speed 20min at room temperature, the rear curing agent that is added is uniformly mixed, then is poured Enter in mold, in 95~110 DEG C of solidification 4h, obtain fire-retardant E~44(such as Fig. 2), fire-retardant E~44 and the epoxy specimens of pure E~44 The comparison of taper calorimetric experimental result such as table 2(35kW/m2Heat radiation), microcapsules anti-flaming smoke-inhibiting agent pair manufactured in the present embodiment The influence result of the epoxy resin mechanical property of E~44 such as table 3.
Table 2: the hot smoke suppressing effect of drop of fire-retardant E~44 and the epoxy resin of pure E~44
Table 3: influence of the anti-flaming smoke-inhibiting agent that embodiment 2 obtains to the epoxy resin mechanical property of E~44
By the experimental data of table 2,3, it is known that, the addition of microcapsules anti-flaming smoke-inhibiting agent manufactured in the present embodiment can efficiently drop The heat release rate peak value (PHRR) of low epoxy resin E~44 reduces nearly 1/2, and average heat release rate (HRR) reduces by 49%, always Heat liberation unit (THR) reduces by 57%；CO yield reduces 45%, and total cigarette yield (TSP) reduces by 71%, and carbon yield increases by 42%, is demonstrated by Excellent fire-retardant and smoke suppressing effect, and microcapsules anti-flaming smoke-inhibiting agent manufactured in the present embodiment is to power such as the tensile strengths of epoxy resin Performance is learned to have no adverse effect.
After carrying out taper calorimetric experiment, pure epoxy tree E~44 and asphalt mixtures modified by epoxy resin E~44 that the present embodiment anti-flaming smoke-inhibiting agent is added As shown in Figure 3 and Figure 4.By Fig. 1,2,3 and 4 it is found that pure epoxy resin plate tests after-combustion totally in taper calorimetric, in addition to corner Place is almost without residue；And carbon left is obvious after sulfonation cross linked ciclodextrines starch capsules fire retarding epoxide resin taper calorimetric experiment Increase, and form expansion, complete layer of charcoal, the layer of charcoal of the complete closure has isolation air, isolation heat, inhibits combustible gas The effect of body release has protective effect to material internal.
Embodiment 3
A kind of sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent of the invention, the microcapsules anti-flaming smoke-inhibiting agent by Interior embedding material and outer cladding capsule layer composition, preparation method specifically comprise the following steps: that (following number is mass parts Number)
(1) suitable quantity of water is added after mixing 40 parts of beta-cyclodextrins and 55 parts of starch, stirs 0.5h under 50 DEG C of constant temperatures, Then the NaOH solution tune PH about 9~11 that mass concentration is 10% is added in 30 parts of epoxy silane crosslinkers, is added dropwise after reacting 2h 0.1mol/L hydrochloric acid tune PH about 6.5 is washed to neutrality after room temperature is cooling, then is dried in vacuo under the conditions of 60 DEG C, through pulverizing 80~120 meshes are crossed afterwards, obtain cross linked ciclodextrines starch；
(2) the cross linked ciclodextrines starch obtained after step (1), according to cross linked ciclodextrines starch: the concentrated sulfuric acid=1:5 matter The concentrated sulfuric acid for being 95% than mass concentration is added is measured, coking 3h is carried out under the conditions of 80 DEG C, is washed with deionized to neutral laggard Row drying, obtains coking charcoal, and by quality dimidiations such as the coking charcoals；
(3) the wherein carbonization at low temperature charcoal obtained after step (2), according to coking charcoal: the concentrated sulfuric acid=1:6 mass ratio is added The concentrated sulfuric acid that mass concentration is 98% carries out sulfonation 2h under the conditions of 80 DEG C, and washing to filtrate is neutrality, and can't detect sulfuric acid Until radical ion, sulfonation coking charcoal is obtained after dry；
(4) it is with mass concentration by another carbonization at low temperature charcoal (the coking charcoal used is porous structure) obtained after step (2) 75% 90 parts of dipping 2h of phosphoric acid solution, 20 parts of urea are then added under ice-water bath and is stirred evenly, and filtering vacuum drying obtains To load coking charcoal；
(5) 20 parts of beta-cyclodextrin are taken, suitable quantity of water is added, stirs 1h under 50 DEG C of constant temperatures, appropriate mass concentration is added For 10% NaOH solution and 15 parts of epoxy silane crosslinkers, after so that it is carried out reaction 1h, the sulfonation obtained after step (3) is added 35 parts of the load coking charcoal 25 parts of coking charcoal and obtained after step (4), carries out being warming up to 60~70 DEG C after mixing evenly, at lump It is dried after shape, 80~120 meshes is crossed after pulverizing, obtain powder；
(6) 80 parts of powder, 5 parts of the addition emulsified wax stirring 0.5h that will be obtained after step (5), adds dodecyl sulphur 5 parts of sour natrium surfactant obtains copolymerization powder, the as interior embedding material with sonic oscillation 1h；
(7) melamine, 37% formalin and distilled water are mixed by 60 parts of quality, 120 parts, 400 parts, tune pH to 8~ 9, stirring is warming up to 70 DEG C, keeps constant temperature 1h, adds Nano-meter CaCO331.5 parts stir evenly；It is trimerization that quality is added after cooling The curing accelerator resorcinol of melamine resin quality 1.5~2.0%, stirs evenly to get Nano-meter CaCO33Melamine pre-polymerization Resin；
(8) by 65 parts of interior embedding material obtained after step 1, dispersion falls into 180 parts of nanometers of atomization in reaction tower CaCO3In melamino-formaldehyde pre-polymerization resin steam fog, make interior embedding material by Nano-meter CaCO33Melamino-formaldehyde pre-polymerization resin Cladding gets up to form coating, then heats with 80~120 DEG C of air-flow, solidifies the coating and dried, cold But evengranular microcapsules anti-flaming smoke-inhibiting agent is obtained afterwards.
Effect detection:
In parts by weight, by 80 parts of sulfonation charcoal microcapsules anti-flaming smoke-inhibiting agent manufactured in the present embodiment and PVC200 parts, DOP64 Part, EVA96 parts, 100 parts of wood powder, 9 parts of stearic acid, 6 parts of paraffin, 60 parts and 30 parts of compound stabilizer of dicalcium powder fast in 80 DEG C of constant temperature Lower stirring takes out the sample stirred evenly in 3 minutes in fast blender, is kneaded on kneading machine while hot, and melting temperature control exists It 140~160 DEG C, after the completion of mixing, waits samples cooling, is then crushed with pulverizer, repeat to crush three times, be ground into tiny Then grain uses trigger squeeze pressing plate, controlled at 160 DEG C, flame-proof PVC wood-plastic board is made in pressure 10MPa.The taper of sample Calorimetric experimental result comparison such as table 4(50kW/m2Heat radiation), microcapsules anti-flaming smoke-inhibiting agent manufactured in the present embodiment is to PVC wood Mould the influence result such as table 5 of mechanical property plate mechanical property.
Table 4: the hot smoke suppressing effect of drop of flame-proof PVC wood-plastic board and pure PVC wood mould plate
From 4 data of table it is found that flame-proof PVC wood-plastic board is greatly improved than the fire prevention smoke suppressing of pure PVC wood mould plate, highest Peak heat release is by 398.9kW/m2Drop to 282.2kW/m2, reduce about 30%；Average heat release rate reduces 33.5kW/m2, The 21% of about pure PVC wood mould plate；Total heat release also reduces by 30.2% than pure PVC wood mould plate.In addition to effectively reducing heat The flue gas release of release, flame-proof PVC wood-plastic board is also reduced, and raw cigarette total amount reduces by 32.4%, YCO than pure PVC wood mould plate and also reduces 28.1%.Illustrate that the microcapsules of the present embodiment can hinder the decomposition and combustion reaction of PVC wood plastic clad plate, increase remaining char, reduces Heat release reduces the release of smog poison gas, has significant flame-retardant smoke inhibition attenuation.
Table 5: influence of the anti-flaming smoke-inhibiting agent that embodiment 3 obtains to flame-proof PVC wood-plastic board mechanical property
5 experimental data of analytical table, after PVC wood mould plate adds the microcapsules anti-flaming smoke-inhibiting agent of the present embodiment, the maximum of material Failing load, static bending strength, bending modulus increase, and show the microcapsules anti-flaming smoke-inhibiting agent of the present embodiment to PVC wood plastic composite wood With particle humidification.

Claims (7)

1. a kind of preparation method of sulfonation cross linked ciclodextrines starch capsules anti-flaming smoke-inhibiting agent, comprising the following steps:
Step 1: after cross linked ciclodextrines starch is made in cyclodextrin and starch, coking is carried out under the action of the concentrated sulfuric acid and is handled To coking charcoal, coking charcoal described in a portion carries out sulfonation and handles to obtain sulfonation coking charcoal, and coking charcoal described in another part is negative It carries phosphoric acid and urea obtains load coking charcoal, then be crosslinked by the sulfonation coking charcoal, load coking charcoal and cyclodextrin anti- Copolymerization powder should be made to get interior embedding material is arrived；
Step 2: by melamine resin and Nano-meter CaCO33It is mixed and made into Nano-meter CaCO33Then melamine pre-polymerization resin will The interior embedding material dispersion obtained after step 1 falls into the Nano-meter CaCO3 of atomization3In melamine pre-polymerization resin steam fog, make interior packet Material is buried by Nano-meter CaCO33Melamine pre-polymerization resin cladding is got up, and is hindered after cured drying to get to the microcapsules Fire smoke suppressant.
2. preparation method according to claim 1, which is characterized in that the step 1 specifically includes following operating procedure:
(1) add water after mixing cyclodextrin and starch, crosslinking is added after 0.5~1.0h is stirred under 40~60 DEG C of constant temperatures Agent, with NaOH solution tune pH to 9~11, reacting after 1~2h with hydrochloric acid tune pH is 6~7, after room temperature is cooling washing to neutrality, It is dried in vacuo under the conditions of 50~60 DEG C again, 80~120 meshes is crossed after pulverizing, obtain cross linked ciclodextrines starch；
(2) concentrated sulfuric acid is added in the cross linked ciclodextrines starch obtained after step (1), coking 2 is carried out under the conditions of 60~80 DEG C ~3h, washing obtains coking charcoal after being dried to neutrality, and the coking charcoal is divided into two parts；
(3) concentrated sulfuric acid is added in a portion coking charcoal obtained after step (2), sulfonation 1 is carried out under the conditions of 80~100 DEG C ~2h obtains sulfonation coking charcoal after dry until washing to filtrate is neutrality and can't detect sulfate ion；
(4) another part coking charcoal phosphoric acid solution obtained after step (2) is impregnated into 1~2h, is then added under ice-water bath Urea stirs evenly, and filtering vacuum drying obtains load coking charcoal；
(5) water is added in cyclodextrin, crosslinking agent is added after stirring 0.5~1.0h under 40~60 DEG C of constant temperatures, uses NaOH After so that it is carried out 0.5~1.0h of reaction, the sulfonation coking charcoal obtained after step (3) and step is added in solution tune pH to 9~11 (4) the load coking charcoal obtained after, is warming up to 60~70 DEG C after mixing evenly, and at being dried after lump shape, 80 are crossed after pulverizing ~120 meshes, obtain powder；
(6) emulsified wax is added in the powder obtained after step (5) and stirs 0.5~1.0h, surfactant is added, with ultrasound 1~2h is vibrated to get interior embedding material is arrived.
3. preparation method according to claim 2, which is characterized in that the cyclodextrin includes alpha-cyclodextrin or β-ring paste Essence；The crosslinking agent includes epoxy silane crosslinker or epichlorohydrin crosslinker；The surfactant includes dodecyl Sulfuric acid natrium surfactant or neopelex surfactant.
4. preparation method according to claim 2, which is characterized in that
In the step (1), the mass fraction of cyclodextrin is 40~50 parts, and the mass fraction of starch is 50~60 parts, crosslinking agent Mass fraction be 20~30 parts, the mass concentration of NaOH solution is 8~10%, and the concentration of hydrochloric acid is 0.1mol/L；
In the step (2), the mass concentration of the concentrated sulfuric acid is 70~95%, and the mass ratio of cross linked ciclodextrines starch and the concentrated sulfuric acid is 1:5~7；
In the step (3), the mass concentration of the concentrated sulfuric acid is 90~98%, and the mass ratio of coking charcoal and the concentrated sulfuric acid is 1:6~8；
In the step (4), the mass concentration of the phosphoric acid solution is 60%~80%, and mass fraction is 80~100 parts；Institute The mass fraction for stating urea is 10~20 parts；The coking charcoal is porous structure；
In the step (5), the mass fraction of cyclodextrin is 20~30 parts, and the mass fraction of crosslinking agent is 10~20 parts, sulfonation The mass fraction of coking charcoal is 20~30 parts, and the mass ratio of sulfonation coking charcoal and load coking charcoal is 1:1~2, NaOH solution Mass concentration is 8~10%；
In the step (6), the mass fraction of powder is 60~80 parts, and the mass fraction of emulsified wax is 2~5 parts, and surface is living Property agent mass fraction be 2~5 parts.
5. preparation method according to any one of claims 1 to 4, which is characterized in that the step 2 specifically include with Lower operating procedure:
A. by melamine resin and Nano-meter CaCO33PH to 8~9 is adjusted in mixing, and stirring is warming up to 70~80 DEG C, constant temperature 1~2h, cold But curing accelerator is added afterwards, stirs evenly to get Nano-meter CaCO33Melamine pre-polymerization resin；
B., the interior embedding material dispersion obtained after step 1 is fallen into the Nano-meter CaCO3 of atomization3Melamine pre-polymerization resin steam fog In, make interior embedding material by Nano-meter CaCO33Melamine pre-polymerization resin cladding gets up to form coating, then with 80~120 DEG C Air-flow heating, solidify the coating and dried, obtain the microcapsules anti-flaming smoke-inhibiting agent after cooling.
6. preparation method according to claim 5, which is characterized in that
In the step a, melamine resin is by melamine, 37% formalin and distilled water 1:2.5~3:6 in mass ratio ~7 mix；The Nano-meter CaCO33Mass fraction be 1~2 part；The mass fraction of the melamine resin be 50~ 70 parts；The curing accelerator is resorcinol, and the additional amount of the curing accelerator is the 1.5% of melamine resin quality ~2.0%；
In the step b, the mass fraction of interior embedding material is 60~80 parts, Nano-meter CaCO33The matter of melamine pre-polymerization resin Measuring number is 100~300 parts.
7. a kind of sulfonation cross linked ciclodextrines starch being prepared such as preparation method according to any one of claims 1 to 6 is micro- Capsule anti-flaming smoke-inhibiting agent.
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